Method for solvent extraction of fatty materials



Fellv 18, E, MORTENSONv METHOD FOR soLvENiTEXTRAcTioN oF FATTYMATERIALS Filed Jan. 28, v1944 conuenserg VACUUM STI l lh

'SETrLmca Boxes TANK I I* Eri-RACT non MIXIN PUMP VESSEL INVENTOR BY /M ATTORNEY NGY WATER Patented Feb. 18, 1947 Y Y METHOD FOR SOLVENT EXTRACTION OF FATTY MATERIALS Everett N. Mortenson, Chicago, Ill., assignor to Industrial Patents Corporation, Chicago, Ill., va corporation of Delaware Application January 28, 1944, Serial No. 520,000`

This invention relates to and has to do particularly with the treatment of a relatively solid carrier material for the removal of oleaginous substances therefrom. 4

The solvent extraction method has been Widely employed for the removal of oleaginous material from solid matter ina relatively dry state. Such methods are impractical, however, when applied to materials containing substantial amounts of water, since the water must be largely removed to avoid the formation of troublesome emulsions of solvent and Water under the conditions of agitation and heat ordinarily employed in the extrac- .tion process. The necessity of preliminarily drying the material to be extracted considerablydeteriorates the oleaginous material by polymerization and decomposition, particularly where such material is of a fatty nature. This operation like- Wise involves the use of special drying equipment and requires large expenditures of heat.

In order to avoid deterioration and facilitate the recovery of oleaginous materials, it has been proposed to extract Wet solids under conditions of heat and agitation to `drive off the water and all or part of the solvent during the process, thereby preventing emulsion formation. In the event that the solvent is substantially removed, it becomes necessary to continuously replenish the supply during the extraction. Likewise, the elimination of the water content by this method requires a tremendous expenditure of heat since not only must the latent heat of vaporization be supplied for the solvent and water, but heat must be furnished to raise the additional solvent to the extraction temperature. This method of extraction is actually closely relatedto the aforesaid dry extraction with solvents since the material is substantially dry after the water has been vaporized. A particular Weakness of thisgmethod is that the extraction is not complete, since a small amount of the miscella remains absorbed inthe pores of the material.

Methods of fat recovery have also been practiced on the dry and wet basis Without the use of solvents. The dry rendering of fatty material has been employed to a great extent in the packing industry as a means of recovering fat from adipose tissue. Also, the recovery of oil from cottonseeds and soy beans by the use ofexpellers is broadly considered a dry rendering process. The Wet method of rendering for the recovery of fatty matter from pork adipose tissue usually rerquires pressure cooking of the adipose tissue in the presence of steam and Water. The application of such prior methods, however, has not been Claims. (Cl. .N50-41.2.8)

satisfactory for the recovery of fats present in relatively small amounts in the solid matter without the substantial deterioration of the fatty material. n

It is an object of this invention to provide a rapidv and eiiicient method Vof "extracting oleaginous substances from solid carrier material containing an appreciable amount of Water.

It is also an object of this invention to provide a method for the elimination of emulsions formed during the extraction of oleaginous substances with solvents.

It is another object of the invention to provide a method for the recovery of oleaginous values Without substantial deterioration thereof.

Other objects and advantages, if not specifically pointed out, will be apparent to those skilled in the art from the following detailed description of what is now considered to be a preferred eme' bodiment of the invention taken in conjunction with the appended drawing. n

, In general, the method of the invention comprises agitating an aqueous slurry of material containing an oleaginous substance in the Vpresence of a solvent for the oleaginous substance` while heating the mixture to a temperaturel below the boiling point of the solvent to substantially extract the oleaginous substance, reduc ing the rate of agitation Without substantially lowering the temperature of the mixture to cause a separation of a solvent layer containing the extracted oleaginous substance and a water layer and recovering'the oleaginous substance by removal of the solvent. It is preferred to employ a solvent having a boiling point higher thanwater and conduct the extraction process at a temperature in the region of the boiling point of vent action until the process is completed.. InA

the event that the extraction is carried out'at temperatures below thefboiling point of the Wa`` means.

During the extraction, emulsion formation may occur to a varying degree depending upon the Water content and the nature of the material being extracted., It has been discovered that reducing the rate of agitation 4without substan y tiallyy loweringY the temperature unexpectedlyv causes the emulsion lto break down with the formation of a solvent layer containing the extracted oleaginous substance and a water layer containing extracted solid matter. Where the extraction is carried out at the boiling point of the water, the emulsion is broken by reducing` 'the boiling rate of the mixture. The solvent layer may then be separated and treated for recovery of the oleaginous materiaL Y The solvent employed in the process will generally depend upon the conditions under which theextraction is to be accomplished in a partie "larv case, as well as the characteristics of the 61; girioos materialto be treated; slncetne extraction is advantageously carried out'at a teme perature at least Vin the region of the boiling p'oin'tQfjvater, solvents immisci'ble withl water andgl'iavjing a boiling point abovethat of water at the pressure employed are preferred.

Solvents which may be successfully employed in ne extractionofy oleaginous materials at tern pe tures above the boiling point of water include diamyl ether, dilisoamyl ether, dib'utylether, diisobutyl ether, di-secondary butyl ether, decano, di'b'utyl ketone, d iis'obu'tyl ketone, dieth'yl ketone,

ietnyl tolueneeietliyl bfenzenes, dip'ropyl ketone,

di`isopropyl ketone', tetramethyl benzene (duethyl lornyl ether, etnylernyl ketone, ethyl benzene', ethylbutyl ketone, methyl butyl ketone, methyl'- isobutyl ketone,1chlorobenzene; toluene, :,Eyleie; and petroleuijnfraetions oistilling within tlie range or about 105 C5250D C. or higher. For most eicient operation, the petroleum vfractions of ,a narrow boiling range,^ suchv las from about 1Q5' C.` 17D 1,5Q C., 110 lC. to 120 C., 150, C. to ,290 (1;, 170 C. to 175 C., ls0 C. to190 C., and 20'0C.' to' 220 C., are preferred and particularly petroleum, frootions boiling alo-ove 150 C. and be vv 250 C. with asnarrow a boiling'r'ange as po ible are best fromthe standpoint of cost, safety and 'solvent powen Where the extraction is' be ,accomplished at temperaturesv below the bo rig point of water, a petroleum fraction have lung `boiling range of from 80"` C. to 110? C. may be, use, By the employment of petroleum fractions' having a relatively narrow boiling range, the' process may beV VStandardized within conside eab'ly narrower limitsV than is possible with one having' s relatlvely wiole -looiline range. Petrofraetio-ns having a relatively low initial boit ing Ipi'i'int 'are undesirable frorn the standpoint of re hazard and, for this reason, those having a n sp point by tlije open oiip method greater than 70j C are preferred.

vExfalrlp'les of oleaginous materials which may be' s uccessfullytreated by the presentV process include ,thefollowing:v

l. Chemically precipitated packing house pr'oteins which have been heat coagulated, concentrated by dewatering but not dried. Such a sludge may run from 5 per ce'nt to 25 per 'cent solids but, in any case, is far too wet forthe application of conventional solvent `extraction methods.

2.,'Sump bottoms Vand storage settlings .from tank Water drawnroff from @Si WI?? .lerllg process, These materials likewise are very high 4 in moisture content and cannot be solvent extracted in the usualway without the formation of troublesome emulsions but may be successfub 1y treated by the present invention.

3. Various earths and inert materials used for thev bleaching, clarification or filtration of fats and oil' s. Il'les'e' materials ordinarily contain almost 2() per cent of fat by Weight' al'ld'v being essentially dry, must be formed into a slurry by the The material containing the oleaginous substance is preferably ground or comminuted and mixed with water to form a fluid slurry. If the material is relatively dry, sufficient Water is pref-- erably added to increase the moisture content to over 20 per cent by weight. Most eflicient extraction of the oleaginous substance is obtained when the moisture content constitutes from about 20 per cent to per cent of the mixture, depending upon the material being treated.

The amount of solvent employed is generally' governed by the amount of fatty or 'greasy substance in the material to be extracted, since, in most cases, a direct relationshipV exists between the concentration of the'fat in the solvent and the stability of the emulsion. It is preferredy to use sufficient solvent to give a low concentration of fat in the solvent medium. Concentrations of fat or greasy matter in the solvent comparable to tlle' percentage concentration of fat or 'greasy matter in the dry solid material have been found to give successful resultsA in Carrying out the present method. When these concentrations are employed, the emulsionI formed during the eX- tlaction process is readily Abroken out on reducing the rate of agitation. It has also been found that good results are obtained when the concentration of fat in the solvent does not exceed l5 to 25 per cent after complete transfer of vrfat from the material to the solvent has been effected.

lIn every case, sufficient solventis used so that,

lard and an equal amount of Water heated to fja- Cllltate InfliXilg are introduced it a vessel I. Tfl wet material is then passed t a centrifugal mixw ing pump 2 to orn a homogeneous tslurry f bleaching earth and water and thereafter, through a conduit 3 to one of two extraction tanks '4 and 5, A branch .conduit 6 serves for re-` v turning all or part of the slurry Vto vessel I for producing a more uniform mixture and valves and v8 for controlling .the relative'flow of material to the aforesaid extraction tanks. The slurry may then be introduced into the extraction .tank 4 through conduit 9 and valve I0, valve I I in conduit I2 leading to the extraction tank 5 being closed. When extraction tank 4 is about half full, valvek Il l is closed. The mixture in vessel I is thereafter circulated continuously through con-y duit 6 to maintain a uniform slurry ofthe spent earth and water. f A'solverlt, preferably one having a higher boilingpoint than water, lis introduced @into extraction tank `4 from a solvent st'crafge tank `|3 by means Oflpump i4 andv conduits rI5 and I6. A' branch conduit I1 is provided for conveying solvent to extraction tank and valves I8 and I9 serve to control the solvent flow through conduits I6 and I 1l respectively.

Tanks 4 and 5 are connectedv by conduits 20 and 2I to a reflux condenser 22 of any known type which may be cooled by a heat exchange medium circulated through coil 23. The reflux condenser is provided with a vent .24 by virtue of which the extraction tanks 4 and 5 are maintained at approximately atmospheric pressure during the extraction process. Heat in the form of steam is supplied to the contents of extraction tanks 4 and 5 through diiusers 25 and 25 which are connected to a steam line 21. Valves 28 and 29. control the supply of steam to diifusers 25 and 26.

When the calculated amount of solvent ha been introduced into' extraction tank 4, valve I8 is closed and steam valve 28 is opened to heat the mixture of slurry and solvent to the vboiling point of the water contained therein. The mixture begins to boil and the vapors to reflux when the sum of the partial pressures of Water and solvent exceed atmospheric pressure. Sufficient heat is supplied in this manner to cause the mixture to boil vigorously. vDuring the ebullition, the two phases become a homogeneous emulsion of small particles and the grease begins to diffuse from the water layer solids into the solvent layer. Since the solvent has a higher boiling point than water, very little solvent distills thereby providing the most favorable euqilibrium condition for complete recovery of the fatty material. Vaporized water and solvent are condensed in condenser 22 and return to the extraction tank 4 via conduit 20. The solvent action is greatly augmented by the vigorously boiling water. When the extraction is substantially complete, the rate of agitation is substantially reduced to break the emulsion. By reducing the supply of steam to about 50 percent or less and allowing the mixture to slowly simmer for a period of time depending upon the nature of the material, the solvent cracks out bringing the dissolved fat with it.

After the emulsion is broken, the mixture separates into two clear cut layers. The top solvent layer containing extracted fatty material is withdrawn through a conduit 30 and valve 3| to a vacuum still 32. Extraction tank 5 is similarly connected with the vacuum' still by conduit 33 and valve 3-4. The vacuum still is ,heated to about 220 F. by steam admitted to coil 35 from the main steam line 21. The solvent vapors distill off from the fat and are carried through conduit 31 to condenser 38 and separatory tank 39, wherein any distilled water is removed through conduit 40 and valve 4i. A vacuum pump 42 is designed to maintain a vacuum of about 26 inches of mercury in the still. The solvent is Withdrawn from the separatory tank through conduit 43 and returned to the solvent storage tank I3 for reuse by a pump 44.

The last traces of solvent may be stripped from the fatty material by a steam jet 36. The recovered fatty material is removed from the system through conduit 45 controlled by a Valve 46.

The lower water layer containing the fat free extracted earth is withdrawn from the extraction tank 4 through conduit 41 and kvalve 48 to settling boxes 49 and allowed to settle. Extraction tank 5 is similarly providedwtih a conduit 50 andvalve 5I connected with conduit 41.` The supernatant water isdrawn. off through line '52 and the earth manually removed from the set` tling boxes and charged into a kiln 53 to be fired and prepared forreuse.

l Fullers earth extracted and treated in the foregoing manner `shows substantially. 100 per centof its` original. bleaching potency- The fattyr materiaLrecovered is not .deteriorated in any way and constitutes. over 9.5 per cent of that contained in the unextracted earth. c

The process may be made substantially continuous by passing the Iwet slurry of material first to the extraction tank 4 and, thereafter, to extraction tank 5. While the charge in one of the extraction tanks is being subjected to extraction, the previously extracted charge in the otherl tank may be treated for recovery of the extracted fatty material and solvent in the vacuum still.v

In a specific example, 1,000 grams of spent fullers earth containing about 20 per cent fatv from the decolorization of lard Were charged into a vessel and treated with low pressure steam to form a slurry. The slurry was charged into extraction tank and 2,000 cubic centimeters of Deobase (a petroleum fraction having a boiling range from 370 F. to 480 F. and a flash point of from 170 1'". to 180 F.) were then added to the extraction tank. The solventvamounted to a ratio of about 154 pounds of solvent per pound of dry earth. Live steam was fed from the steam line at a suiciently rapid rate to thoroughly mix the earth, water and solvent and vigorously agitate the resulting mixture.Y A rapid rate of extraction was maintained` for `about 3() minutes during which time avery intimate contact` of the solvent,.water, earth and grease was effected. At the end of this time, the amount of steam fed intothe tank was markedly reduced until avery gentle boiling of the mixture took place for V20 to 30 minutes. The emulsion then suddenly broke and the solvent layer cracked out cleanly, carrying the grease With it. The solvent containing the fatty material was subjected to vacuum distillation in the still, followed by injection of steam to` completely strip off the sol, vent. The solvent was recovered for reuse in the process. The fatty material was drawn off at the vbottom of the still and found to constitute a yield of about 98 per cent of the original fat content of the earth.

It is important that the rate of ebullition be substantially reduced during the cracking out period to completely 'break the emulsion. If the agitation and heating are discontinued, a complete separation does not occur.

Although the process has been described in connection with the recovery of fatty material from-decolorizing earths, it is readily applicable to the treatment of any material containing oleaginous substances Whether the object is'the recovery of the oleaginous matter or the purification of the carrier. It is to be understood that the kconditions employed may vary over a wide range depending upon'the nature of the oleaginous sub- 1. The method of recovering voleaginous substance from material containing the oleaginous substance, which comprises rapidly agitating an aqueous slurry of said material in the presence of a solvent for the oleaginous substance having a boiling point higher than water; said agitation being performed While maintaining a temperature at least in the region of the boiling point of water to substantially extract said oleaginous substance from the material but with the formation of an emulsion of solvent, oleaginous substance, and water; then reducing the rate of agie tation without substantially lowering the temperature of the mixture to cause arbreaking of the emulsion and the separation of a solvent layer containing the Yextracted oleaginous substance from the aqueous slurry;.and thereafter recovering the oleaginous substance by the removal of the solvent. Y

2. The method of recovering oleaginous substance from material containing the oleaginous substance, rwhicln'comprises rapidly boiling an aqueous slurry of said material containing from about 20 per cent to 95 per cent Water in the presence of a water immiscible solvent for the oleaginous substance having a boiling point higher than water whereby an emulsion is formed of the solvent, water, and the oleaginous substance; condensing and refluxing the vapors flowing from the mixture to substantially extract said oleaginous substance from the material in the presence of a substantial quantity of water; then reducing the rate of boiling without substantially .lowering the temperature of the mixture to cause the breaking of the emulsion and separation of a solvent layer containing the extracted .oleaginous f emulsion of solvent, water, andoleag-inous substance is produced; reducing the rate of heat input to cause a reduction in the -boiling action whereby to ieffect the breaking of 'the emulsion;

and then separating the `solvent layer containing. the extracted oleaginous lsubstance Ifrom the aqueous slurry. f

4. The method of recovering oleaginous substance from Amaterial containing the oleaginous substance, which comprises heating an aqueous slurry of said material to the boiling lpoint ofthe mixture in the presence of a water immiscble solvent forthe oleaginous substance, the solvent having aboiling point higher than water; reilux-3 ing and relatively violently agitatingthe mixture to'substantially extract thecleaginou's substance from said material under conditions which .produce 'an emulsion of solvent, water, and oleaginous substance; the amount vof solvent being at least suflicient to provide a maximum concentration not greater than about 15 per cent of the oleaginous substance in the solvent; reducing the rate of heat input to reduce the degree of agitation materially while 'maintaining the boiling tem*- perature to cause the breaking of the emulsion and separation of a solvent layer containing the extracted oleaginous substance from the aqueous slurry.

5. The method of recovering oleaginous substance from material containing the oleaginous substance, which comprises vigorously agitating a comminuted aqueous slurry of said material in the presence of a water immiscible solvent for the oleaginous substance, said solvent having a boiling point higher than water; performing said agitation while maintaining the temperature of the slurryat its boiling point and refluxing the vapors flowing from the mixture; maintaining at least suicient solvent in the mixture to provide amaximum concentration not greater than labout 15 per cent of the oleaginous substance in the solvent until extraction is substantially complete; said agitation forming an emulsion between the solvent, the water, and the oleaginous substance;` and then reducing the rate of heat input to substantially reduce the rate of agitation while maintaining the temperature of the bath to cause the breaking of the emulsion-and separation of a solvent layer containing the extracted oleaginous substance from the aqueous. slurry.

' `6. The method lof recovering oleaginous substance from material containing the oleaginous substance, which comprises agitating an aqueous slurry of said material inthe presence of a solvent for the oleaginous substance while heating the mixture to a temperature below the boiling point of the solvent to substantially extractthe oleaginous substance but with the formation of an emulsion of solvent, oleaginous substance, and

water; and reducing the rate of agitation Without substantially lowering the temperature of the mixture to cause a breaking of the emulsion and a separation of a solvent layer containing the extracted oleaginous substance from the aqueous slurry; and thereafter recovering the oleaginous substance by removal of the solvent.

7. The method of recovering oleaginous substance from material Vcontaining the oleaginous substance, which comprises agitating an aqueous slur-ry of said material in the presence of a solvent for 'the oleaginous substance consisting of a petroleum fraction distilling within ther range of abouty 105 C. 'toabout'250 C-; simultaneously heating the mixture to a temperature below the and thereafter recovering the oleaginous sub- Y stance by removal of lthe solvent.

V8. The method of recovering oleaginous Asubstance lfrom material containing the oleaginous substancawhich comprises agitating an aqueous f slurry of said 'material in theY presence of a 'solvent for "the oleaginous substance Shaving a relatively narrow boiling Jrange'ffalling within the 'limits of' above 150 C. and below 250 C.; simultaneously heating the mixture to a temperature below the boiling point of the solvent to substantially extract the oleaginous substance but with the formation of an emulsion composed of water, solvent, and oleaginous substance; and then reducing the rate of agitation without substantially lowering the temperature of the mixture to cause a breaking of the emulsion and a separation of a solvent layer containing the extracted oleaginous substance from the aqueous slurry; and thereafter recovering the oleaginous substance by removal of the solvent.

9. The method of recovering oleaginous substance, which comprises heating an aqueous slurry of said material to the boiling point of the mixture in the presence of a water immiscible solvent for the oleaginous substance, the solvent having a boiling point higher than that of water; relatively violently agitating the mixture to substantially extract the oleaginous substance from said material; said heating and agitation causing the formation of an emulsion composed of oleaginous substance, water, and solvent; the quantity of the solvent present being at least sufficient to provide a maximum concentration not greater than about 15% of the oleaginous substance in the solvent; reducing the rate of heat input to substantally reduce the rate of agitation While maintaining the boiling temperature to cause the breaking of the emulsion and separation of a solvent layer containing the extracted oleaginous substance from the aqueous slurry.

10. The method of recovering oleaginous substance from material containing the oleaginous substance, which comprises heating an aqueous slurry of said material to the boiling point of the mixture in the presence of a water immiscible solvent for the oleaginous substance, the solvent having a boiling point higher than water; relatively violently agitating the mixture to substantially extract the oleaginous substance from said material under conditions which produce an emulsion of solvent, water, and oleaginous substance; the amount of solvent being at least suiiicient to provide a maximum concentration notV greater than about 15 per cent of the oleaginous substance in the solvent; reducing the rate of heat input to reduce the degree of agitation materially While maintaining the boiling temperature to cause the breaking of the emulsion and separation of a solvent layer containing the extracted oleaginous substance from the aqueous slurry.

EVERETT N. MORTENSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,503,751 Dreymann Aug. 5, 1924 807,567 Maywald Dec. 19, 1905 183,098 Adamson Oct. 10, 1876 

